KR101042370B1 - water dispersable conductive high molecule polymer-carbon nanotube and water-soluble stabilized emulsion comprising the same, and method for fabricating the same - Google Patents

Abstract

The present invention relates to a conductive polymer-carbon nanotube composite by a miniemulsion polymerization process, a method for preparing a stabilized water-soluble emulsion composed thereof.

In the present invention, by polymerizing a monomer which is a raw material of a conductive polymer using a miniemulsion polymerization process, a conductive polymer-carbon nanotube composite having a carbon nanotube and a conductive polymer material together and a stabilized water-soluble emulsion composed thereof are provided.

The conductive polymer-carbon nanotube composite according to the present invention is a material having flexibility, transparency and improved electrical conductivity, and has limitations of existing materials in various fields such as nano-electronic devices such as organic light-emitting diodes. As a material to overcome, various applications can be expected.

Conductive, Polymer-Carbon Nanotubes, Composites, Water Soluble, Emulsion

Description

Water dispersable conductive high molecule polymer-carbon nanotube and water-soluble stabilized emulsion comprising the same, and method for fabricating the same}

The present invention relates to a conductive polymer-carbon nanotube composite, a stabilized water-soluble emulsion composed of the same, and a method for manufacturing the same. More specifically, the present invention relates to a mini emulsion polymerization process that can be applied to various industrial fields by overcoming the limitations of existing materials. The present invention relates to a conductive polymer-carbon nanotube composite and a stabilized water-soluble emulsion composed thereof.

Carbon nanotubes are largely anisotropic in structure, and have various structures such as single wall, multi-wall, and rope, and exhibit the properties of conductors and semiconductors according to their wound shape. The energy gap varies, and it has a quasi one-dimensional structure, resulting in a unique quantum effect.

The unique structure and physical properties of carbon nanotubes show the versatile characteristics of flat display devices, integrated memory devices, secondary batteries and ultracapacitors, hydrogen storage materials, chemical sensors, high strength / light weight composite materials, and static electricity, which are essential for information and communication equipment. It has excellent applicability to removal composite materials, electromagnetic shielding materials, etc., and has the possibility of exceeding the limitations of existing devices, and various studies have been made.

However, carbon nanotubes show many problems in dispersibility of particles by coagulating by van der Waals forces. As a solution, dispersion using solvent, dispersion using surfactant, dispersion using acid treatment and Many studies have been made on dispersion using an electrolyte.

Recently, studies on dispersing carbon nanotubes using β-1,3-glucan have been conducted by Numata et al. (Numata M .; Asai M; Kaneko K .; Bae AH; Hasegawa T .; Sakurai K .; Shinkai S., J. . Am. Chem. Soc., 127, 5875 (2005).) have been reported by, addition of poly (3,4-ethylenedioxythiophene) (PEDOT ) nanoparticles using a β-1,3-glucan conductive polymer Studies on the preparation of aqueous solutions have also been made by Li et al. (Li, C .; Numata M .; Hasegawa T .; Fujisawa T .; Haraguchi S .; Sakurai K .; Shinkai S., Chemistry Letters , 34 (11) , 1532 (2005).

However, no studies have been made to prepare carbon nanotubes and PEDOT composites, which are conductive polymers, by miniemulsion polymerization using β-1,3-glucan.

The present invention overcomes the limitations of existing materials as a material having flexibility, transparency, and improved electrical conductivity, and is applicable to various industrial fields such as sensors, electrode materials, nanoelectronics, and the like. It is an object to provide a water-soluble emulsion.

In order to achieve the above technical problem, the present invention provides a stabilized water-soluble emulsion composed of a conductive polymer-carbon nanotube composite, characterized in that produced by a mini emulsion polymerization process.

The conductive polymer is characterized in that it comprises Poly (3,4-ethylenedioxythiophene) (PEDOT).

The carbon nanotubes may include multi-walled carbon nanotubes (MWCNTs).

It is characterized by using β-1,3-glucan to disperse the carbon nanotubes and the conductive polymer.

The β-1,3-glucan is characterized in that it is used to extract from Sparassis crispa.

As the surfactant used in the miniemulsion polymerization process, any one of anionic surfactant (dodecylbenzene sulfonic acid), cationic surfactant (decyltrimethylammonium bromide), nonionic surfactant (polyoxyethylene-11-decylether) (Lutensol, BASF AG) It is characterized in that it is used.

As the oxidizing agent for oxidative polymerization of the emulsion in the miniemulsion polymerization process, the oxidizing agent is characterized in that any one of ammonium persulfate, iron (III) p-toluenesulfonate, cerium (IV) sulfate is used.

On the other hand, according to another aspect of the present invention for achieving the above object, using a β-1,3-glucan, preparing a carbon nanotube in a well dispersed solution in an aqueous solution; A method of preparing a stabilized water-soluble emulsion composed of a conductive polymer-carbon nanotube composite, comprising: polymerizing a monomer which is a raw material of a conductive polymer using a miniemulsion polymerization process in a state where the prepared carbon nanotube is present. This is provided.

In addition, according to another aspect of the present invention for achieving the above object, an oil-phase solution containing a monomer which is a raw material of carbon nanotubes and a conductive polymer material to form a complex therewith, water containing a surfactant and water Provided is a method for preparing a stabilized water-soluble emulsion composed of a conductive polymer-carbon nanotube composite, wherein a solution of -phase is put into a reactor and a miniemulsion polymerization is carried out under nitrogen atmosphere.

On the other hand, according to the present invention, there is provided a water-soluble emulsion, characterized in that formed by containing the conductive polymer-carbon nanotube composite.

In addition, according to the present invention, there is provided a conductive polymer-carbon nanotube composite dispersed in water, which is produced by the above method.

In addition, according to the present invention, there is provided a conductive polymer-carbon nanotube composite, which is made by vacuum drying in a state where the miniemulsion polymerization is completed by the above method.

According to the present invention, a method for producing a conductive polymer-carbon nanotube composite by a miniemulsion polymerization process can be provided.

That is, according to the present invention, by using a β-1,3-glucan to prepare a carbon nanotube in a solution well dispersed in an aqueous solution and polymerize the monomer as a raw material of the conductive polymer in a miniemulsion polymerization process conductive polymer-carbon nanotube It can provide a method for producing a composite.

In addition, according to the present invention, an emulsion composed of a carbon nanotube / PEDOT composite prepared by a miniemulsion process using a surfactant shows excellent stability over a long period of time.

Since the conductive polymer-carbon nanotube composite according to the present invention is in a stabilized water-soluble emulsion state, the application field can be broadly expanded by applying various coating technologies, and specifically, existing materials in various fields such as sensors, electrode materials, and nanoelectronics fields. Various industrial applications can be expected as new materials that can overcome these limitations.

Hereinafter, a conductive polymer-carbon nanotube composite (hereinafter, also referred to as a "composite") and a method of manufacturing the same according to the present invention will be described in detail.

The conductive polymer-carbon nanotube composite according to the present invention is prepared using a miniemulsion polymerization process. The mini emulsion polymerization process is widely used in the chemical field and is an emulsion of oil-in-water (O / W) containing droplets forming oil phase in water.

The miniemulsion polymerization process used in the present invention helps to keep the particles in a stable state by helping the particles not to coagulate with each other, to make the particles small and round, and to make the polymerization reaction in a solution. Suitable for the production of tube composites.

Carbon nanotubes are classified into multi-walled carbon nanotubes (MWCNTs), double-walled carbon nanotubes, single-walled carbon nanotubes, and the like according to the number of walls. It is not limited.

According to the present invention, carbon nanotubes and conductive polymer composites may be prepared by dispersing carbon nanotubes in an aqueous solution using β-1,3-glucan and polymerizing monomers, which are raw materials of conductive polymers, in the presence of the carbon nanotubes. It can be.

Materials that can be complexed with carbon nanotubes include conductive polymers such as polypyrole, polyaniline, and poly (3,4-ethylenedioxythiophene), but in particular Poly (3,4-ethylenedioxythiophene) (aka "PEDOT"). ) Is preferably prepared as a composite with carbon nanotubes by the method of the present invention.

In the present invention, an oil-phase solution containing a carbon nanotube and a monomer, which is a raw material of a conductive polymer material to be complexed thereto, and a water-phase solution containing a surfactant and water are placed in a reactor under nitrogen atmosphere. The polymerization is carried out. In the case of performing the miniemulsion polymerization, it is preferable to carry out the polymerization by stirring for 48 hours at a condition of about 35 ° C temperature.

An oxidizing agent is required for the polymerization reaction. Carbon nanotubes and monomers are put in a reactor, temperature and atmospheric conditions are adjusted, and an aqueous oxidizing agent is administered to the reactor to perform polymerization.

In addition, polymerization is carried out by different kinds of oxidizing agents and surfactants. The types of surfactants used here are anionic surfactants (eg dodecylbenzene sulfonic acid), cationic surfactants (eg decyltrimethylammonium bromide), nonionic surfactants (eg polyoxyethylene-11-decylether) (Lutensol: product name, BASF AG: Oxidants include ammonium persulfate, iron (III) p-toluenesulfonate and cerium (IV) sulfate.

After the polymerization reaction is completed, the obtained composite is vacuum dried at 60 ° C. with a vacuum oven dryer to prepare a desired conductive polymer-carbon nanotube composite.

Hereinafter, the present invention will be described in detail through examples. However, the scope of the present invention is not limited by the following examples.

The conductive polymer-carbon nanotube composite prepared in the following examples is an infrared spectrophotometer (FTIR spectrometer), field emission scanning electron microscope (FE-SEM), transmission electron microscope (TEM), particle size analyzer (PSA), X-ray diffraction ( XRD) pattern and the like.

For reference, SEM and TEM photographs of MWCNTs are disclosed in (a) of FIG. 1, and (b) SEM (Scanning Electron Microscope) of MWCNT-Poly (3,4-ethylenedioxythiophene) composites prepared using the same. Transmission Electron Microscope (TEM) photography is disclosed.

Example  One:

Anionic surfactant and ammonium persulfate  Using oxidants Mini Emulsion  Polymerized MWCNT - Poly (3,4- ethylenedioxythiophene ) Preparation of the complex.

3.6 g of dimthylsulfoxide (DMSO) and 1.5 g of β-1,3-glucan (MW =) ( Sparan , Hanabiotech Co.) were mixed and stirred. Again, 3 g of DMSO and 0.3 g of MWCNT (CM-95, Iljin Nanotech) were mixed and stirred. DMSO mixed with β-1,3-glucan and DMSO mixed with CNTs were mixed and stirred. To this solution, 3.553 g of 3,4-ethylenedioxythiophene (EDOT) was added, followed by stirring to form an oil-phase.

0.3264 g of dodecylbenzene sulfonic acid (DBSA) and 84 mL of deionized (DI) -water were mixed and stirred to form a water-phase.

2.1286 g of ammonium persulfate (APS), an oxidant, was dissolved in 10 mL of deionized (DI) -water to prepare an oxidizer aqueous solution. The oil-phase solution was gradually added to the water-phase solution while stirring. The beaker containing the mixed solution was soaked in ice water and cooled sufficiently and treated with ultrasonifier (Model 450, Branson) for 10 minutes. (25% duty cycle, power 3)

After putting the above solution into the reactor, the temperature was raised to 35 ° C., an oxidizer aqueous solution prepared by dissolving in DI-water in advance, and then polymerized under nitrogen atmosphere for 48 hours. After the polymerization was completed, vacuum drying was performed for 8 hours to prepare a MWCNT-Poly (3,4-ethylenedioxythiophene) complex.

Example  2:

Cationic Surfactants and Ammonium persulfate  Using oxidants Mini Emulsion  Polymerized MWCNT - Poly (3,4- ethylenedioxythiophene ) Preparation of the complex.

MWCNT-Poly (3,4-ethylenedioxythiophene) complex was prepared in the same manner as in Example 1, except that 0.2803 g of decyltrimethylammonium bromide (DETAB) was used instead of DBSA.

Example  3:

Non-ion  Surfactant and ammonium persulfate Using oxidants Mini Emulsion  Polymerized MWCNT - Poly (3,4- ethylenedioxythiophene ) Preparation of the complex.

MWCNT-Poly (3,4-ethylenedioxythiophene) complex was prepared in the same manner as in Example 1 except that 0.684 g of a polyoxyethylene-11-decylether ( Lutensol , BASF AG) was used instead of the DBSA.

Example  4:

Anionic surfactant and iron (III) p - toluenesulfonate Using oxidants beauty  Performing the emulsion emulsion MWCNT - Poly (3,4- ethylenedioxythiophene ) Preparation of the complex.

MWCNT-Poly (3,4-ethylenedioxythiophene) complex was prepared in the same manner as in Example 1, except that 6.3687 g of iron (III) p- toluenesulfonate was used instead of ammonium persulfate (APS).

Example  5:

With anionic surfactants cerium ( IV ) sulfate Using oxidants Mini Emulsion  Polymerized MWCNT - Poly (3,4- ethylenedioxythiophene ) Preparation of the complex.

MWCNT-Poly (3,4-ethylenedioxythiophene) complex was prepared in the same manner as in Example 1, except that 3.123 g of cerium (IV) sulfate was used instead of ammonium persulfate (APS).

As described above, in the present invention, the carbon nanotubes and the conductive polymers are dispersed using β-1,3-glucan, and the polymers are well dispersed in the aqueous solution by polymerizing the conductive polymers in a miniemulsion polymerization process in the presence of carbon nanotubes. It was confirmed that the conductive polymer-carbon nanotube composite can be prepared.

1 is a SEM (Scanning Electron Microscope) and TEM (Transmission Electron Microscope) photograph of the MWCNT-Poly (3,4-ethylenedioxythiophene) complex, (a) is a SEM and TEM photograph of MWCNT, (b) of the present invention Picture of MWCNT-PEDOT Composite According to Example

Claims (11)

Stabilized water-soluble emulsion composed of a conductive polymer-carbon nanotube composite, which is prepared by a miniemulsion polymerization process. The method of claim 1, The conductive polymer is a stabilized water-soluble emulsion composed of a conductive polymer-carbon nanotube composite, characterized in that it comprises Poly (3,4-ethylenedioxythiophene) (ie, PEDOT). The method of claim 1, The carbon nanotube is a stabilized water-soluble emulsion consisting of a conductive polymer-carbon nanotube composite, characterized in that it comprises a multi-walled carbon nanotube (MWCNT). The method of claim 1, Stabilized water-soluble emulsion consisting of a conductive polymer-carbon nanotube composite, characterized in that for using β-1,3-glucan to disperse the carbon nanotubes and the conductive polymer. The method of claim 4, wherein The β-1,3-glucan is a stabilized water-soluble emulsion composed of a conductive polymer-carbon nanotube complex, characterized in that extracted from Sparassis crispa. The method according to claim 1 or 2, As the surfactant used in the miniemulsion polymerization step, A stabilized water-soluble emulsion composed of a conductive polymer-carbon nanotube composite, wherein any one of anionic surfactant, cationic surfactant, and nonionic surfactant is used. The method according to claim 1 or 2, As the oxidizing agent for the oxidative polymerization of the emulsion in the miniemulsion polymerization process, The oxidizing agent is a stabilized water-soluble emulsion composed of a conductive polymer-carbon nanotube composite, characterized in that at least one of ammonium persulfate, iron (III) p-toluenesulfonate, and cerium (IV) sulfate is used. using β-1,3-glucan, preparing carbon nanotubes into a well dispersed solution in an aqueous solution; A method of preparing a stabilized water-soluble emulsion composed of a conductive polymer-carbon nanotube composite, comprising: polymerizing a monomer which is a raw material of a conductive polymer using a miniemulsion polymerization process in a state where the prepared carbon nanotube is present. . Into the reactor, an oil-phase solution containing carbon nanotubes and a monomer, which is a raw material of a conductive polymer material to be complexed with the carbon nanotubes, and a water-phase solution containing a surfactant and water are placed in a reactor under nitrogen atmosphere. Method for producing a stabilized water-soluble emulsion consisting of a conductive polymer-carbon nanotube composite, characterized in that by performing a mini emulsion polymerization. A conductive polymer-carbon nanotube composite dispersed in water, which is prepared by the method of claim 8 or 9. A conductive polymer-carbon nanotube composite, which is made by vacuum drying in a state where the miniemulsion polymerization is completed by the method according to claim 8 or 9.

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